Walter bruck



v halogen,- H V l, i

In my copending application for an provement in production ofchloroanthrai Patented Mar. 1, 1932 r -WALTER,BRUCK,DE MANNHEIM, GERMANY; Assreivo n TO GENERAL 'ANILiNE worms,

INC OF SEW YORK, Y, A CORPORATION OFJDELAWARE T .7

a HALOGEN'ATED ANTHRZJLQUIVNONEBENZACRIVEDONE NoDrawing. Application-fil ed.Apri1 24} 1930;Seria1 No; 147,083, and. inl Germany January 25, 1929.

'Ihe present i nyention relates tothe pro-c duction of anthraquinone-2.1(N) bengacri clones in which at least the hydrogen atoms of the benzene nucleus are -su'bstituted quinoneacridone Seru- No. .421,Z2 l filed Janu ary 18, 1930, 0t Whichthe present application is a ,continuationin part, I have describe d a process for the production an anthraquin one {2. 1( N)-benzacridon;e {containing about 5 Ia-toms of chlorine by trcating l'c-phenylf in inoanthraquinone containing a methyl groupin ortho position to the imino group inan organicsolvent Witha chlorinating agent, separating the chlorination productmore readily soluble inorganic solvents from the reaction :mixture "and splitting oif chlorine or hydrogen chloride from the separated product. The product containing about 5 atomsgof'chlorine yields on boiling with di-. ethylaniline an -anthraquinone 2.'l (N) ;-ben

zacrid-one containing about 4; atoms of chlorine Which producton chlorination again yields the initial materialcontaini g ,5 atoms of chlorine; f

V I have now found that a similar product and products having a structure similar to that of the aforesaid chloroanthraquinone- 2.l(N)-benzacrido ne, are obtained by-condensingl-halogenanthraquinone-2-carboxylic acid or derivatives thereof with 2.3.L5-tetral halogen 'anilines'having aifree .6 -position or y by condensing l-ha'logena'nthraquinones with 7 free 2-position With'2-amido-benzoic acids in i which the hydrogen atomsofthe benzene nu- V cleus are substituted halogen, acridonei +0 ring closure thenbeing efi'ected;

The products thus obtained correspond to v the formula :7

Products of the same structure containing halogen atoms are alsoiobtained by bromi hating Bz 3.5-dihalogen-anthraquinone-2.1-'

(N )-benzacrid0nes Which are obtainable in the aforesaid man-nerby, employing a3.5-dihalogenaniline [as condensing component.

WV hen chlorinating the-said initial material pentahalogen derivatives are-obtained containing a chlorine atom in the l-position of V the anthraquinone nucleus which chlorine atom can be replaced by hydrogenibyboiling V the pentachlforo. derivative with. diethylanir line. The aforesaid pentahalog'en {derivlae tiv'es are also obtained when starting 'Wltll" a" 1A dichloranthraquinOne-Q-carboxylic Y acid and condensing it with a 2 .3.4.5 -t etrahalogen anilinei or With-1a 3-.5- dihalogen" aniline and halogenatingf thelcondensationproducti The} v halogen atom the l-p ositilonofthe amhm; quinone nucleus causesa surprisinglyfiiarked are dyestuffs which in additionto excellent hange bf-ft h h s t blu it l rr uct Example 1 38 parts of 1-chloroanthraquinone-2-carboxylic acid benzyl ester of the formula:

18 parts of m-dichloroaniline of the'formula:

thraquinone 2.1 benzacridone of the formula: 01

is obtained analytically pure by crystallization of the crude product from nitrobenzene. It dissolves in concentrated sulphuric acid giving an orange yellow solution and furnishes a violet vat from which cotton is dyed orange shades.

Ewample 2 20 parts of l-chloroanthraquinone-2-carboXylic acidbenzyl ester are heated for 4 hours at from 185 to 195 C. with 9 parts of 2.8.4.5-tetrachloroaniline, 6.2 parts of anhy- 6 parts of sodium carbonate and 1 part of copper powder are heatedin 500 parts of butyl alcohol for 24 hours at about 180 C. in an iron pressure Vessel. The reaction product is filtered ofi by suction after cooling, washed with alcohol and boiled up with d1- lute hydrochloric acid and dried.

10 parts of the 1-dichloroanilidoanthraquinone-Z-carboxylic acid benzyl ester thus obtained corresponding to the formula:

(Ill

O1 H-N O I are suspended in 50 parts of dry nitrobenzene. After the addition of 5 parts of acetic acid anhydride the whole is stirred for about 2 hours at from 95 'to 100 C. The whole is then diluted with 100 parts of drynitrobenzene, about 0.8 part of concentrated sulphuric acid are addedand the whole is kept at from 90 to100 C; for another 2 hours.

The reaction mixture is freed from IllDIO- benzene by distillation with steam and acid constituents are removed by extraction with dilute caustic soda; The Bz -3.5-dichloroandrous sodium acetate, 0.3 part of copper oxide and 30 parts of nitro-benzene' After cooling themelt is poured into 200 parts of concentrated sulphuric acid, care being taken that the temperature does not rise above 50 C. After stirring for 1 hour the solution is poured into water and the nitrobenzene is driven "off with steam. The remaining tetrachloroanilidoanthraquinone 2- carboxylic acid is filtered off by suction and dried.

23 parts of the acid are stirred for 2 hours at 150 C. with 90 parts of dry nitrobenzene and 11 parts of acetic acid anhydride, the melt is diluted with 90 parts of dry'nitrobenzene and 2.7 parts of concentrated sulphuricacid are gradually added at from 95 to 100 C. The temperature is then kept the same for about 4 hours, and the whole is then allowed to cool and the reaction product is filtered off by suction. It is washed with nitrobenzene, dilute caustic soda is added, and the product is freed from nitrobenzene and alkali-solubleimpurities by steam distillation and subsequent filtration.

The Bz-2.3.4.5-tetrachloroanthraquinone- 2.1 (N) -benzacridone thus obtained corresponding to the formula:

' concentrated sulphuric acid giving an orange is a reddish yellow substance which only dissolves in organic solvents of high boiling point with great difficulty. It crystallizes from trichlorobenzene in long orange yellow,

matter needles. The color of the solution in concentrated sulphuric acidis orange yellow, the vat is Violet and the dyeings on cotton an orange yellow of excellent fastness.

Example 3 The orange yellow crystals of Bz-3.5-di chloro Bz 2.4 dibromoanthraquinone-21 (N) benzacridone corresponding to the formula:

V V O1 are filtered off. The product may be recrystallized from trichlorobenzene, itdissolv'es in yellow solution and dyes cotton fast orange shades form a Violet Vat.

Example 4 V 2 parts of the pentachloroanthraquinone- 2.1 (N) -benzacrid0ne obtainable'according to 1 my copending application Ser. No. 421,727

are boiled for about 1 hour in 20 parts of.

diethylaniline. -The coloration of the solution which initially is'red turns to orange yellow and brown yellow crystals separatev After cooling, thereaction product isv out. filtered off, washed with diethylaniline, ethyl alcohol and water and may be recrystallized from trichlorobenz ene in order to obtain it.

quite pure. The propertiesof the dyestuif thus produced are the same as those of the product described inEXample 2.

I V Emamplei I 22 parts of 1.4dichlor0anthraquinone-2- carboxylic acid benzyl ester are heated for 4% hours at from 180 to 190 Cpw ith 10 parts of 2.3.4.5-tetrachloroaniline, 6 parts of V anhydrous sodium acetate, 0.3 part of copper oxide and parts of nitrobenzene. After;

cooling the melt is introduced into200 parts of concentrated sulphuric acid and. is stirred forl hour at from; $0409 (1'. The solution is then poured into water and thenitrobenzene is, expelled with steam.;' The remaining 1 tetrachloroanil ido e 4 chloroane. thraquinone-2-carboXylic acidis filtered off by suctionand dried: T v V 22 partsfof the said acid are-stirred 01 parts of dry nitrobenzene and 10 partsvof acetic acid anhydride. The melt is then diluted with parts of dry nitrobenzene and o 1. hours at from 145 to l55:;G-.with-80 1' 2.5 parts ofconcentrated sulphuric acid are] slowly introduced at from to G.' The whole is keptkat the same temperature for about. 3 hours, and is then allowed to cool when the reaction product is filtered ofi by suction. It iswashed. with nitrobenzene and i V is freed from-solvent by steam distillation. I

The product corresponding to the formula:

7 dissolvesin concentrated sulphuric acid givingan orangered coloration, it gives a violet vat and yields oncotton a brilliant bluish roseish'ade ofexcellent fastness I The dyestuif may becrystalliZed from tri'chlorobenzene,' in, which as in all organic solyent-s itisi soluble] only with great 'dif-j ficulty; and is thus obtained injprismat'ic needles. 1

Example 6" r ;,23? part or the Bz-2.3AQ5-tetraehloroan-Q thraquinone; 2.1 berizacridone prep ared accordingto Example 2 are suspended in 600 'partsof dry nitrobenzene-and after the addition of 2'partsof iodineabout 90 parts of sulphuryl chloride are allowed to run in while] stirring at from 909to 100 C. during the course of 1 hour. The whole is stirred at the same temperature for about-5 hours, the eX- filtered 101f by suction. after cooling. It is washed with nitrobenzene and freed. from fcessofsulphuryl chlorideisexpelled with a 'str'eainof-dry air and-the reaction product is solventby steamdistillationu The product thus obtained may -be"crystjallized from j trichlorobenzene.- It corresponds with the dyestuff described in the foregoing example as regardsits-tinctorial andotherflproperties; "Ewe 27210267 "one-211 {behzacridong (obtainable from -V1411iChloroanthraquinoheQ carboxylic'{acid 4.3 of "4- Bz-3.5 trichloroanthraquin- Y by condensation with 3.5-dichloroaniline and subsequent acridone ringclosure) are stirred with 04 part of iodine and 120 parts of dry nitrobenzene, and then'9 parts of sulphuryl chloride are gradually introduced at from 95 to 100 C. The whole is stirred for about 3 hours at the same temperature and is then allowed to cool. Thereactionproduct of the formula:

is filtered off by suction and isolated in the usual manner.

Example 8 After the addition of 0.7 part of iodine to a suspension of 13 parts of the Bz-3.5-dichloranthraquinone-2.1 (N) -benzacridone obtainable according to Example 1 in 300 parts of dry nitrobenzen e, 30 parts of sulphuryl chloride are gradually introduced at from 90 to 100 C. The whole is stirred for about 4 hours at the same temperature, cooled and the reaction mass filtered off by suction. The working up is carried out in the same manner as in the foregoing examples. The product may be crystallized from trichloroben- Zene and is the pentachloroanthraquinone- 2.1(N)-benzacridone hereinbefore described according to analysis'and properties.

What I claim is:

1. As new articles of manufacture tetrahalogen derivatives of anthraquinone-2.1- (N)-benzacridone in which four halogen atoms are present in the benzene nucleus and which dissolve in concentrated sulphuric acid giving orange yellow solutions and dye cotton from violet vats orange shades.

2. As a new article of manufacture Bz- 2.3.4.5-tetrachloroanthraquinone-2.1 (N) -benzacridone crystallizing from trichlorobenzene in orange yellow needles, dissolving in concentrated sulphuric acid to give an orange yellow solution and dyeing cotton from a violet vat orange shades.

3. As a new article of manufacture Bz- 3.5-dichloro Bz-EZA-dibromo anthraquinone- 2.1(11 )-benzacridone crystallizing from trichlorobenzene in orange yellow crystals, dissolving in concentrated sulfuric acid to give an orange yellow solution and dyeing cotton from a violet vat fast orange shades.

In testimony whereof I have hereunto set my hand. 3

I WALTER BRUCK. 

